Composition of matter and method of producing



Patented Mar. 2, 1937 UNI-TED STATES COMPOSITION OF MATTER AND METHOD OFPRODUCING Irvin w. Humphrey, Wilmington, DeL, assignor to HerculesPowder Company, Wilmington, DeL, a corporation of Delaware No Drawing.

20 Claims.

'This invention relates to a new composition of matter and method forits production.

, It is known that maleic anhydride can be neutralized either with analkali, forming an inorganic salt, or with an alcohol forming an ester.

But it would not be expected that maleic anhydride, which is acidic,would react with an ester of abietic acid, which is neutral, forminga-new chemical compound; an abietic-maleic anhydride. The additioncompound may be formed as the result of reaction occurring between thetwo unsaturated bonds of the abietic acid ester and the unsaturatedlinkage of the maleic anhydride, yielding an ester of abietic acid whichcontains a reactive anhydride group. Abietic acid is a monobasic acidbut the compound formed by treating an ester of abietic acid, as forexample, methyl abietate, with maleic anhydride may be termed methylabietate-maleic anhydride. This new compound may be considered as themono-ester of a new resin acid containing the abietyl radical, itscarboxyl group being neutralized by methanol, and which possesses areactive anhydride group. Uniting the rosin ester with 5 maleicanhydride serves a dual purpose since this method of synthesis not onlyafiords a method of obtaining esters of a new acid possessing theabietyl group, but also results in reducing the unsaturation of theabietic acid ester, thus ren- 3 0 dering it more stable to light andair.

By virtue of possessing a reactive anhydride group, the variousabietate-maleic anhydride compounds may be reacted with an alkali, assodium hydroxide, calcium hydroxide, potassium carbonate, etc., or witha reactive oxide as calcium oxide, ethylene oxide, etc., or with a suiteable alcohol such as methanol, ethyl, butyl, amyl, propyl, stearol,laurol, a glycol, as ethylene glycol, propylene glycol, diethyleneglycol, etc., glycerol, borneol, fenchyLethylene glycol monoethyl ether,hydroabietyl, cyclohexanol, benzyl, tetrahydrofurfuryl, mixtures ofalcohols, etc.

The abietate-maleic anhydride compound may be employed in protectivecoatings such as lacquers, varnishes, etc., but it is preferably firstconverted into one of its more complex esters, by treatment with apolyhydric alcohol, such as ethylene glycol or glycerol. An excess ofthe polyhydric alcohol may be added over that required to combine withthe anhydride group; any free hydroxyl groups thus-introduced may beesterified by treatment with an organic acid Application March I, 1935,Serial No. 9,805

(01. zen-s) furoic, hydroruroic terpinene-maleic-anhydride,butadiene-maleic anhydride, etc., or mixtures of suitable organic acids,yielding a product which is also adapted for use in protective. coatingsand in plastics. Drying or semi-drying oils may be '5 added, if desired.

The method in accordance with this invention for production of the newcomposition or resinous material embodying this invention will appearfrom the following description and examples of 10 the production of thenew composition.

For the production of the composition embodying this invention, maleicanhydride may be reacted with any suitable ester of abietic acid, such,for example, as an ester of a monohydric or poly- 15 hydric alcohol, asethyl abietate, methyl abietate, propyl abietate, bornyl abietate,tetrahydrofurfuryl abietate, lauryl abietate, stearyl abietate,hydroabietyl abietate, butyl abietate, amyl abietate, a glycol abietate,glycerol abietate, benzyl 20 abietate, cyclohexanol abietate, ethyleneglycol monobutyl abietate, phenyl abietate, diethylene glycol abietate,etc. An inorganic abietate as sodium, calcium, aluminum, etc. may becombined with maleic anhydride. 25

The reaction between the ester of abietic acid and maleic anhydride willbe brought about by heating say at a temperature within the range C.-250C. or more, preferably within the narrower range C.-200 C., for from 1to 15 hours. In the reaction, if desired; though not necessarily, acatalyst may be used, as for example, paratoluene sulfonlc acid, benzenesulfonic acid, or other suitable catalyst. If desired, though notnecessarily, the reaction may be carried out in the presence of asolvent such, for example, as xylene, toluene, tetralin, butyl acetate,or other suitable solvent, heating under pressure, if desired, andremoving solvent by distillation after the reaction.

As illustrative of the preparation of a composition embodying thisinvention in accordance with the method embodying this invention, forexample, 82 grams of ethyl abietate are heated with 20 grams of maleicanhydride at a tempera- 45 ture of C. for eight hours. The reactionproduct may then be distilled at a temperature of about 225 C.-250 C.under about 5-10 mm. pressure to remove any unreacted ethyl abietate andmaleic anhydride. The product will amount 50 to about 85 grams ofresinous material slightly softer than rosin, having an acid number ofabout 130 and a saponification number of about 250. The resinous productwill be fairly pale in color and. can be partly distilled under about 5mm.- 55

' pressure using a bath temperature of about 250 C'. to 300 C.

As a further illustration, for example, 80 partsof glycerol abietate, A.N. 5.8, thiocyanate value 5 72.8, are heated with 25 parts of maleicanhye dride at 170 C. for 6 hours. Distilling oil the non-reacted maleicanhydride will leave a hard resinous product, A. N. 134, S. N. about 220thiocyanate value 1.6.

of the new composition the time factor may be reduced or increased, or,in other words, the reaction accelerated or the time required thereforextended, by proceedingat a higher. or lower 1 temperature than given inthe above illustration. Thus, for example, proceeding at a temperatureof about 190 C. the reaction may be efiected in about two to four hoursor, on the other hand,

proceeding at a lower temperature than that 2 given in the aboveillustration, as for; example,

a temperature of 150 C., the reaction may re guire about four to'abouteight hours.

' Generally one mol. of maleic anhydride will be used per mol. of anabietic acid ester, if the latter is derived from a monohydric alcohol,but

. the molar proportion of the anhydride may range about 0.8 to 1.2,depending chiefly upon the reac tivity. oithe isomers presentin theabietic acid ester. In event the ester is "a diabietate it, will 0normally require twice as much maleic anhydride, while atriabietate'will times as abietate.

As has been indicated, in proceeding for the preparation of the product,the maleic-anhydride and the ester of abietic acid may be reacted insolution in a suitable solvent. Where the reaction is eiiected in thepresence of a solvent the above procedure may be followed, the productso after the reaction has been effected being separated from the solventby distillation.

Compositions in accordance with this invention, as is indicated, may beformed by reacting various esters of abietic acid with maleic anhy- 45dride following the procedure given above, more particularly, withreference to the composition formed by reacting ethyl abietate andmaleic anhydride.

The-product, if desired, maybe hydrogenated 50 to increase itssaturation. Hy drogenation may be efiected by, for example, passinghydrogen through the product under a pressure of about 200-15000 poundsat a suitable temperature, say a temperature of about 1'75, C.-200 C.,at which 55 temperature the product will be fluid. In conmuch anhydrideper mol... as a mononection with hydrogenation, an active hydrogenationcatalyst, as for example, nickel,= platinum;

or other suitable hydrogenation catalyst, should be used.

The reaction product may, if desired, be neutralized with an alcohol, asfor example, a monohydric alcohol or. a polyhydric alcohol and, ifdesired, though not necessarily, the alcohol treated product may besubjected to treatment with, 65 for example, an organic acid to effectesterification of any free hydroxyl groups introduced as a result oftreatment with an excess of alcohol. In connection with treatment of thereaction product with an alcohol, an esterification cata- 70 lyst, asfor example, toluene sulfonic acid, suifuric acid, etc. may be used. IWhere the treatment is with certain monoiiydric alcohols, such as butyl,benzyl, amyl alcohol, the treatment will involve heating the alcohol Itogether with the reaction product under atmos-,

In carrying outthe method for the preparation usually taire three phericpressure at a suitable temperature, say

within the range 120 C.-225 C. On the other **,.hand, where thetreatment :is with a lower ali- -phatic alcohol, such as methyl, ethylalcohol, or the like, the treatment generally will involve heating at asuitable temperature, say within the range'about 150 C.250 C. undersuitable pressure, for example, 200-1000 pounds, and where the treatmentis with a polyhydric alcohol, as ethy1ene glycol, glycerol,pentaerythrite, sorbitol, etc., the treating will be at a temperature ofabout 200 0-275." 0. The product may be partially esterified with apolyhydric alcohol and esteriiication completed with a monohydricalcohol.

'Many of the abietate maleic anhydride compounds may be partiallydistilled under vacuum, say about 5 mm. pressure, makinga preliminarycut to' separate any unreacted abietate and maleic anhydride and thendistilling up to a bath temperature of about 300 C. making cuts ifdesired at about'260 C. and 300 C; and leaving a residue. Either thedistillates or the residue may be separately treated with alcohols.

As illustrative, the-reaction product of methyl ,abietate with maleicanhydride was subjected to partial distillation removing 20% by heatingto 250 C.260 C. under 5 mm. pressure. 100 parts of the residue wasreactedwith parts of glycerol under air reflux for 15-hours at 220C.-230 4 C. The product had an acid number of and a drop melting pointof about 88 C. Ethyl abietate-maleic anhydride similarly treated withglycerol exhibited an acid number of and melted around 90 C.

As further illustrative, 200 parts of the residue 7 of a methylabietate-maleic anhydride condensate after distillation off of 20% asabove, was

refluxed with 150 parts, by weight, of butanol and 28 parts of 94%sulfuric acid for 40 hours,

yielding a soft resin.- In a similar experiment 150 parts of methylabietate-maleic anhydride with 150 parts, by weight, of methanol and 25parts of sulfuric acid were refluxed for hours and then thoroughlywater-washed, yielding a soft resin with a. dropmelting point of about-In carrying out the method embodying-this invention for the productionof a new composir tion, it will be understood that the temperatures andranges of temperatures given above are for purposes of illustration andthat I do not contemplate limitation of my invention thereto,

.efiect the reaction indicated and the selection or anyiparticulartemperature within operable limits will be governed largely by the timefactor desired. It" will also be understood that maleic acid. may bereacted with the abietate instead of maleic anhydride, and that themethod can be carried out with esters oi resin acids,

since any'temperature may be used which will other than abietic acid,whose unsaturated bonds have-the capacity for forming an additioncompound with maleic anhydride. i

This application is a continuation in part 01' application for U. S.Patent of Irvin W. Humphrey, Serial No. 561,003, filed September 3, 1931now Patent 2,025,947.

What I claim and Patent is: I

1. A synthetic resin comprising a reaction product of an alcohol with aproduct of the reaction of an abietic acid ester and maleic anhydride.

2. A synthetic resin comprising a reaction product of an alcohol with aproduct of the redesire to.protect by Letters action of a neutralabietic acid ester and maleic anhydride.

3. A synthetic resin comprising a reaction product or a monohydricalcohol with a product of thereaction of an abietic acid ester andmaleic anhydride. 1

4. A synthetic resin comprising a reaction product of a polyhydricalcohol with a product of the reaction of an abietic acid ester andmaleic anhydride.

5. A, synthetic resin comprising a reaction product of ethyl alcoholwith a product of the reaction of an abietic acid ester and maleicanhydride.

6. A synthetic resin comprising a reaction product of methylalcohol witha product of the reaction of an abietic acid ester and maleic anhydride.

"I. A synthetic resin comprising a reaction product of glycerol with aproduct of the reaction of an abietic acid ester and maleic anhydride. V

8. A synthetic resin comprising a reaction product of an alcohol with apartially hydrogenated' product or the reaction of an abietic acid esterand maleic anhydride.

9. A synthetic resin comprising a reaction product of amonohydricalcohol with a partially hydrogenated product of thereaction of anabietic acid ester and maleic anhydride.

10. A synthetic resin comprising a reaction product oi a polyhydricalcohol with a partially hydrogenated product of the reaction of anabietic' acid' ester and maleic anhydride,

11. A synthetic resin comprising a reaction product of an organic acidwith a product of the reaction of an abletic acid ester and maleicanhydride with an alcohol.

12. A synthetic resin comprising a reaction 40productotanorganicacidwithapartiall h drogenated product of the reactionof an abietic acid ester and maleic anhydride with alcohol.

13. The method oi producing a synthetic resin which includes reacting anabietic acid ester with maleic anhydride, treating the reaction productwith an alcohol in quantity in excess of that required to neutralize thereaction product and esteriiying the excess alcohol.

14. The method of producing a synthetic resin which includes reacting anabietic acid ester with maleic anhydride, treating the reaction productwith an alcohol in quantity in excess of that required to neutralize thereaction product and esteriiying excess alcohol with an organic acid.

15. The method of producing a synthetic resin which includes reacting anabietic acid ester with maleic anhydride, treating the reaction productwith a polyhydric alcohol in quantity in excess of that required toneutralize the reaction prod uct and esteriiying the excess alcohol.

16. The method of producing a synthetic resin which includes reacting anabietic acid ester with maleic anhydride, treating the reaction productwith a monohydric alcohol in quantity in excess of that required toneutralize the reaction product and esteritying the excess alcohol.

1'1. A synthetic resin comprising a reaction product of an alcohol witha product oi the reaction of a rosin acid ester and maleic anhydride.

18. A coating composition including the product called for in claim 1and a-solvent.-

19. A coating composition including the product called for in claim 1, anon-volatile lacquer ingredient and a solvent.

20. A coating composition including the product called for in claim 1and a non-volatile varnish ingredient.

IRVIN W.

